Yellow azo dye.



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JOI-IANN HUISMANN, F COLOGNE, GERMANY, ASSIGNOR TO SYNTHETIC PATENTS 00., INC., 01? NEW YORK, N. Y., A CORPORATION OF NEW YORK.

YELLOW AZO DYE.

No Drawing.

To all whom it may concern:

Be it known that I, J OHANN HUISMANN, doctor of philosophy, chemist, citizen of the German Empire, residing at Cologne, Germany, have invented new and useful Improvements' in Yellow Azo Dye, of which the following is a specification;

I have found a new process for the production of new and valuable azo dyes by thiazoledisulfonic acids arylamids.

combining the diazo compounds of aminowith acetoacetic- The new coloring matters dye cotton in pure yellow shades of excellent fastness to light. They are after being dried and pulverized yellowish powders soluble in water and in concentrated sulfuric acid generally with a yellowish coloration; yielding upon reduction with stannous chlorid and hydrochloric acid an a1ninothiazoledisul-- fonic acid having most probably one sulfonic group in ortho position to the amino group, the other component being split up.

The new aromatic aminothiazoledisulfonic acids can be produced by heating preferably in vacuo dehydrothiotoluidin, its homologues or substitution products or the corresponding primulin compounds, such as the sulfo'acids of dehydrothiotoluidin and the new dehydrothiotoluidin acids described in application Serial No. 842,459, with one molecule of sulfuric acid by the so-called baking process and sulfonating the resulting aminothiazolemonosulfonic acids, or by heating preferably in oaouo dehydrothiotoluidin, its homologues or substitution products and the corresponding primulin compounds with 2 molecules of sulfuric acid or with an excess of 2 molecules of sulfuric acid by the so-called baking process, or by heating preferably in some the known monosulfonic acids of dehydrothiotoluidin, its homologues a substitution products or the corresponding primulins with one molecule of sulfuric acid or an excess of one molecule of sulfuric acid by the so-called baking process. The new compounds have Specification of Letters Patent.

Patented Nov. 9, 1915.

Application filed November 5, 1914. Serial No. 870,453.

probably the one sulfonic group in ortlio position to the amino group.

The following example is an illustration for the production of the new sulfonic acids :-2-CLO parts of dehydrothiotoluidin are intimately mixed with a solution of 147 parts of monohydrated sulfuric acid in water and then evaporated to dryness. The powdered product thus obtained is then heated in an oil bath for 45 hours in vacuo to temperatures of from 235-250 C. in a. vessel provided with a stirrer and a downwardly inclined condenser. The process is complete as soon as the distillation of water ceases. The product is dissolved in water with the addition of alkali.

The sodium salt of the new dehydrothiotoluidin-monosulfonic acid crystallizes from the filtered liquid in colorless leaflets. The acid forms a yellow diazo compound soluble in water with difiiculty. 320parts of the dehydrothiotoluidin-monosulfonic acid thus obtained are slowly introduced'into 1500 parts of monohydrated sulfuric acid at a temperature below C. Subsequently 3000 parts of fuming sulfuric acid (65 per cent. of S0 are added and the mixture is kept at 80 to 90 C; during 12 hours until a test portion is soluble in hot water. The mass of the reaction is then poured into ice water and the precipitate is filtered off. The dehydroth-iotoluidindisulfonic acid 'crystallizes from water in yellow leaflets.

at 25 C. to an aqueous suspension of 207' parts of aceto-acetic-ortho-anisidid containing 300 parts of soda. When the combination is finished the mixture is heated until the dyestuif is completely dissolved and the latter is then precipitated from the hot solution by addition of common salt. The new dye having most probably in the shape of the sodium salt the formula:

is after being dried and pulverized a yellow powder soluble in water and in concentrated sulfuric acid with a yellow coloration; and yielding upon reduction with stan'nous chlorid and hydrochloric acid the new 'dehydrothiotoluidin disulfonic acid containing most probably one sulfonic group in ortho position to the amino group, the other component being split up. It yields on cotton beautiful greenish-yellow shades very fast to light; In the same way other of the new aromatic aminothiazoledisulfonic acids such as for instance dehydrothio-metaxylidin-disulfonic acid, the primulin-disulfonic acids, prepared according to the above described baking process, may be used.

Instead of the accto-acetic-arylamid mentioned in the example, its homologues and substitution products, such as for instance the aceto-acetic-meta-xylidid, aceto-acetic chloro anilid, para anisidid, cresidid (meta aceto acetylamido para inethoxytoluene) can be used as coupling components.

I claim l. The herein described new azo dyesbeing derived from new aminothiazoledisultonic acids having most probably one sulfonic group ifl-wprtho position to the amino group and an ceto-acetic-arylamid, which are after being dried and pulverized yellowish powders soluble in Water and in concentrated sulfuric acid generally with a yellowish coloration; yielding upon reduction with stannous chlorid and hydrochloric acid an aminothiazolc-disulfonic acid having most probably one sulfonic group in ortho position to the amino group; the other com ponent being split up; and dyeing, cotton pure yellow shades of excellent fastness to light, substantially as described.

. 2. The herein described new azo dyes being derived from the disulfonic acid of an component being split up; and dyeing cotton pure yellow shades of excellent fastness to light, substantially as described. 3. The herein described new azo dyes being derived from the disulfonic acid of 'a p. aminophenyl methyl benzothiazole compound having most probably one sulfonic group in ortho position tolthe amino group and an aceto-acetic-arylamid, which are after being dried and pulverized yellowish powders soluble in water and inconcentrated sulfuric acid generally with a yellowish coloration; yielding upon reduction with stannous chlorid and hydrochloric acid the disulfonic acid of a u-aminophenyl-methylbenzothiazole compound having most probably one sulfonic group in ortho position to the amino group, the other component being split up; and dyeing cotton pure yellow shades of excellent tastness to light, substantially as described. I

l. The herein described new azo dyes being derivedfrom the disulfonic acid of an aminoarylbenzothiazole compound having most'probably one sulfonic group in ortho position to the amino group and. an aceto- 'acetyl-alkyloxy-arylamid which are after being dried and pulverized yellowish powderssoluble inwater and in concentrated sulfuric acid generally with a yellowish coloration; yielding upon reduction with stannous chlorid and hydrochloric acid the di-. sulfonic acid of an aminoarylbenzothiazoledisulfonic acid having most probably one sulfonic group in ortho position to the amino group, the other component being split up; and dyeing cotton pure yellow shades of excellent fastness to light, substantially as de- I scribed.

5. The herein described new azo dyes being derived from the disulfonic 'acid'of an aminoarylbenzothiazole compound having most probably one sulfonic group in ortho position to the amino group and an acetoacetylamido-oxybenzene compound which are ,after being dried and pulverized yellowish powders soluble in water and in conc ntrated sulfuric acid generally with a yello 'ish coloration; yielding upon reduction wi h stannous chlorid and hydrochloric acid the disulfonic acid of an ami'noarylbenzothiazole disulfonic acid having most probably one sulfonie group in ortho position to the amino group, the other component being split up; and dyeing cotton pure yellow shales of excellent fastness to light, substantially as de scribed.

6. The herein described new azo dyes being derived from the disulfonic acid of'a p. aininophenyl 111ethylbenzothiazole compound having most probably one sulfonic group in ortho posit-ion tdithe amino group and an aeeto-acetylainido-a'lkyloxy-benzene compound, which are after being dried and pulverized yellowish powders soluble in water and in concentrated sulfuric acid gen,- erally with a yellowish coloration; yielding upon reduction with stannous chlorid and hydrochloric acid the disulfonic acid of a p. aniinophenyl methylbenzothiazole com pound having nost probably one sulfonic group in ortho position to the amino group,

the other component being split up; and

dyeing cotton pure yellow shades of excellent fastness to light, substantially as described.

-7. The herein described new azo dyes being derived from the disulfonic acid of uaniinophenyl inetliylbenzothiazole having most probably one sulfonic group in ortho position to the amino group and an acetoacetyla1nido-inethoxybenzene, which are after being dried and pulverized yellowish powders soluble in water and in concentrated sulfuric acid generally with a yellowish coloration; yielding upon reduction with stannous chlorid and hydrochloric acid the disulfonic acid of u-aininophenyl-inethylbenzothiazole having most probably one sulfonic group in ortho position to the amino group, the other component being split up; and dyeing cotton pure yellow shades of excellent fastness to'light, substantially as described.

8. The herein described new azo dye having most probably in the shape of its sodium salt the formula:-

witnesses.

' JOHANN HUISMANN. \Vitnesses J. I). ZIESEAKE, Ann SCIIOENTIIAL. 

